Unsaturated zwitterionic surface active compounds

ABSTRACT

Zwitterionic surface active compounds are provided having the following formula: WHEREIN R1 represents an unsaturated or saturated aliphatic group having six to 24 carbon atoms, R2 and R3 each represent an alkyl group having one to six carbon atoms, and Z represents nitrogen or phosphorus. These compounds have valuable surface active properties that make them especially useful as detergent compounds.

United States Patent Barbera 1 June 6, 1972 [54] UNSATURATED ZWITTERIONIC SURFACE ACTIVE COMPOUNDS [72] Inventor: Melvin A. Barbera, Mount Healthy, Ohio [73] Assignee: The Procter & Gamble Company, Cincinnati, Ohio 22 Filed: Mar. 31, 1970 [21] Appl. No.: 24,330

[56] References Cited UNITED STATES PATENTS 3,594,411 7/1971 Kite ..260/50l.12

Primary Examiner-Bemard Helfin Assistant Examiner--Michael W. Glynn Attorney-Julius P. Filcik and Richard C. Witte [57] ABSTRACT Zwitterionic surface active compounds are provided having the following formula:

wherein R represents an unsaturated or saturated aliphatic group having six to 24 carbon atoms, R and R each represent an alkyl group having one to six carbon atoms, and Z represents nitrogen or phosphorus.

These compounds have valuable surface active properties that make them especially useful as detergent compounds.

4 Claims, No Drawings UNSATURATED ZWITTERIONIC SURFACE ACTIVE COMPOUNDS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to zwitterionic surface active compounds which are useful as detergents. The zwitterionic surface active compounds are characterized by having an unsaturated double bond located in the molecule between the anionic and cationic groups.

2. Prior Art Zwitten'onic or internally neutralized surface active compounds having-both anionic and cationic groups are kno They are usually depicted as having a formula R,R R K in which the Rs are alkyl or alkylene groups (R always being saturated aliphatic) and Xis COO or S No previous disclosure has been found of a surface active compound having R representing a group CH -CH CH-Cl-l It is this unique molecular arrangement which distinguishes the compounds of the present invention from prior art zwitterionic surface active compounds. It has been surprisingly discoveredthat the presence of the double bond contributes unexpectedly to the detergent properties of this molecule.

SUMMARY OF THE INVENTION The compounds of the present invention'have the formula in which R represents an unsaturatedor saturated aliphatic hydrocarbon group having six to 24 carbon atoms, and R and R each represent an alkyl group having one to six carbon atoms.

This class of compounds is illustrated by the following specificexamples:

4-( N ,N-dimethyl-N-hexade cyl-ammonio )-2-butenel -sulfonate; 4-( N,N-dimethyl-N-alkylammonio)-2-butenel -sulfonate, the alkyl group derived from tallow fatty alcohol; 4- N,N-diethyl-N-hexadecylammonio )-2-butenel -sulfonate; 4- (N,N-diethyl-N-tetradecylammonio )-2-butenel -sulfonate; 4- (N,N-dimethyl-N-alkylammonio )-2-butenel -sulfonate, the alkyl group being derived from the middle cut of coconut fatty alcohol; 4-( N ,N-dimethyl-N-octadecyla.mmonio )Z-butenel sulfonate; 4-(N-2-hydroxyethyl, N-methyl, N-tetradecylammonio)-2-butene-l-sulfonate; 4-(N,N-dimethyl-N- dodecylammonio-2-butene-l-sulfonate; 4-(N,N-dimethyl-N- hexadecylphosphonio)-2-butene-l-sulfonate; 4- (N,N- dimethyl-N-alkylphosphonio)-2-butene-l-sulfonate, the alkyl group derived from the middle cut of coconut fatty alcohol; and 4-( N,N-diethyl-N-hexadecylphosphonio Z-butenel -sulfonate. Specific reference to the above compounds is given only for the purpose of illustration, and it will be appreciated that many other similar variations may be used in this invention so long as the general formula requirements are observed.

The preferred compounds of this invention are 4-(N,N- dimethyl-N-hexadecyl-ammonio )-2-butenel -sulfonate; 4- N,N-dimethyl-N-alkylammonio )-2-butenel-sulfonate in which the alkyl group is tallow alkyl which approximately consists of a mixture of 66 percent C 30 percent C 4 percent C or in which the alkyl group is middle cut coconut fatty alkyl which approximately consists of a mixture of 2%C 66%C 23%C and 9%C It is preferred that R, and R be selected from methyl, ethyl, propyl, isopropyl, butyl and ethanol.

The unsaturated zwitterionic compounds of the present invention can be made by any convenient method or process. For example, they can be prepared by reacting tertiary amines or phosphines with butene sultones. The butene sultone can be from any source but a ready source is by a sulfonation reaction between l,3-butadiene and an SO -,-dioxane complex.

An SO -dioxane complex can be prepared by the following procedure:

EXAMPLE 160 g. were added to a mixture of 212 g. dioxane and 588 g. ethylene dichloride. A white solid precipitate which formed was removed by filtering. The precipitate was added to 650 g. dioxane, the mixture was heated to 60 C. and butadiene was bubbled in until the solids were reacted. A two phase liquid resulted. The bottom phase, a yellow oil, was added slowly to 474 g. dimethyldodecylamine and 1,308 g. acetone. This mixture was refluxed at 59 C. and amine values were taken to follow the reaction. Time 0" minutes on amine values is after addition; theoretical value is 56.

Time Amine Value 0 minutes 43 30 minutes 40 minutes 42.4 minutes 41.9 42.5

300 minutes The material was then chilled in a 0 F. box overnight and the white solids removed by filtering and washedwith acetone. The solids were dissolved in a 50 percent 3 A alcohol in water solution to 20 percent solids level. The pH was raised to about 9 with 50 percent NaOH in' order to free the amine from the salt form. This was then filtered to remove the sodium salts and washed with petroleum ether then dried to a solids form. The material was then redissolved to a 62 percent volatiles- 38 percent solids level with water. Analysis confirmed a reaction product of 4-(N-dodecyl-N,N-dimethyl)-2-butene-l-sulfonate.

The discovery that the introduction of one double bond into the radical between cation and anion groups of a zwitterion as described herein produces a compound having surface active performance superior to that of its saturated four carbon counterpart was totally unexpected. The double bond, believed to be the cis-stereoisomer, apparently allows positioning of the charged zwitterionic groupings in such a manner as to enhance the surface activity of the unsaturated compounds beyond that of their saturated counterparts.

In preparing detergent compositions, especially valuable as laundering compositions, it is desirable to use the unsaturated zwitterionic surface active compounds of this invention in admixture with detergency builder compounds. Excellent compositions consist of an unsaturated zwitterionic detergent compound of this invention and at least one detergency builder selected from inorganic or organic alkaline builders in a proportion by weight of detergent to builder of :1 to 1:20 and preferably from 5:1 to 1:10. These compositions provide best overall laundering results including soil removal and whiteness maintenance results when used in washing solutions having a pH 6.5 to 11.5, preferably 7 to 11, optionally 8.5 1 1.

Water soluble inorganic alkaline builder salts which can be used in this invention alone or in admixture are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Ammonium or substituted ammonium, e.g., triethanol ammonium, salts of these materials can also be used. Specific examples of suitable salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium and potassium pyrophosphate, sodium and ammonium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium orthophosphate and potassium bicarbonate. The preferred inorganic alkaline builders according to this invention are alkali metal tripolyphosphates for built granular compositions.

Examples of suitable organic alkaline sequestrant builder salts used in this invention alone or in admixture are alkali metal, ammonium or substituted ammonium, aminocarboxylates, e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2- hydroxyethyl)-ethylenediaminetriacetates, sodium and potassium nitrilotriacetates and sodium, potassium and triethanolammonium N-(Z-hydroxyethyl)-nitrilodiacetates. Mixed salts of these polycarboxylates are also suitable. The alkali metal salts of phytic acid, e.g., sodium phytate are also suitable as organic alkaline sequestrant builder salts (see US. Pat. No. 2,739,942). Sodium ethane-l-hydroxy, ldiphosphonate, and sodium citrate can also be used as builders either alone or in mixtures with other builder compounds. Other suitable builders include methylene and ethylene diphosphonates and their derivatives, ethane-l-hydroxy-l, l ,2- triphosphonate, sodium itaconate, and sodium polymaleate and the like.

The unsaturated zwitterionic surface active compounds of the present invention can also be used in combination with other detergent materials selected from anionic synthetic detergents, nonionic synthetic detergents and ampholytic and zwitterionic synthetic detergents.

A laundering method incorporating the discovery of the present invention can be practiced in a number of different ways. Preferably the washing step is followed by rinsing and drying the fabrics. The washing solution can be prepared by adding the granular, tablet or liquid detergent composition prepared according to this invention to any container which contains water at a temperature ranging from about 40 F. to to about 200 F., usually about 80 F .160 F. The detergent composition concentration in solution can range from about 0.05 percent to 0.50 percent by total weight, and should be added in sufficient amount to provide a concentration of at least 0.005 percent of the zwitterionic detergent compound. The fabrics can be added to the container or washer before or after the washing solution is added. As is usual in a washing step, the fabrics are then agitated in the detergent solution. While the period of time may vary, an automatic agitator type washer, generally employs a washing cycle which ranges from 8 to minutes.

After the washing step, the washing liquor is drained off or the fabrics are separated from the liquor and thereafter the fabrics are rinsed in clean water. The fabrics can be rinsed as many times as desired in order to insure that washing liquor is removed. Using an automatic washer, it has been found that about four spray rinses and one deep rinse are usually sufficient for this purpose. Between and after rinsing steps, the bulk of the rinse water is usually drawn from, or spun out of the fabrics. After rinsing, the fabrics are dried. Although rinsing and drying are usual and desirable steps, the important advantage of the invention is achieved in the washing step.

The following compositions will illustrate the manner in which the zwitterionic surface active detergent compounds of this invention can be used. Included are both liquid and granular formulations. It will be understood, however, that the examples are not to be construed or limiting the scope of conditions claimed hereinafter. These compositions are useful in automatic washers and conventional type washers as well as hand washing operations.

EXAMPLE OF GRANULAR BUILT DETERGENT COMPOSITION 7% 4( N,Ndimethyl-N-hexadecylammonio )-2- butene-l-sulfonate 50% sodium nitrilotriacetate 5% sodium xylene sulfonate 7% sodium silicate (Na O:SiO,=l 22.5) 16% fluorescent dye .2% perfume .02% benzotriazole 20.62% sodium sulfate 10% water and minor amounts of miscellaneous material EXAMPLE OF BUILT LIQUID DETERGENT COMPOSITION 12% 4-( N,N-dimethyl-N-alkylammonio* )-2- butene- 1 -sulfonate 20% tetrapotassium pyrophosphate 3.8% sodium silicate (Na O:SiO =l l .6) 8.5% potassium toluene sulfonate .3% sodium carboxymethyl hydroxy ethyl cellulose 12% fluorescent dye .l5% perfume .02% benzotriazole 55.1 1% water alkyl referring to the R group derived from the middle cut of coconut fatty alcohol (2% m. 66% C 23% C 9% C EXAMPLE OF BUILT LIQUID DETERGENT COMPOSITION 22% 4-( N,N-dimethyl-N-tetradecylammonio )-2- butenel -sulfonate 19% tetrapotassium pyrophosphate 3.8% sodium silicate (Na O:SiO =l :16)

8.5% potassium toluene sulfonate .3% sodium carboxy methyl hydroxy ethyl cellulose .2% perfume .02% benzotriazole 46.18% water and minor amounts of miscellaneous EXAMPLE OF BUILT LIQUID DETERGENT COMPOSITION 12% 4-(N,N-dimethyl-N-alkylammonio* )-2- butenel -sulfonate 19% tetrapotassium pyrophosphonate 3.8% sodium silicate (Na O:SiO l:l.6)

8.5% potassium toluene sulfonate .3% sodium carboxy methyl cellulose .2% perfume 56.20% water alkyl referring to the R group obtained from tallow futty alcohol (66% C 30% m. 4% Cu) d O hers BUILT DETERGENT COMPOSITION y firing to the R, group obtained from tallow fatty alcohol (66% C 30% 4% C and others.

EXAMPLE OF LIQUID BUILT DETERGENT COMPOSITION 4-(N,N-dimethyl-N-alkylammonio*)-2- butenel -sulfonate 60% sodium pyrophosphate 6% sodium silicate (Na O:SiO,=l :2.5) 2% sodium toluene sulfonate .3% sodium carboxy methyl cellulose l 1.3% water Balance miscellaneous (fluorescers, perfume, antitamish agents, sodium sulfate, etc.)

alkyl referring to the R group obtained from tallow fatty alcohol (66% C 30% m. 4% C and others.

EXAMPLE OF GRANULAR BUILT DETERGENT COMPOSITION 17% 4-( N,N-diethyl-N-alkylammonio* )-2-butenel-sulfonate 45% sodium citrate 6% sodium silicate (Na O:SiO =l :2.5) .5% sodium carboxy methyl cellulose 28% sodium sulfate 3.5% water alkyl referring to the R, group derived from the middle cut of coconut fatty alecho] 2% c 66% c 23% c,., 9% c EXAMPLE OF LIQUID BUILT DETERGENT COMPOSITION 4-(N,N-diethyl-N-hexadecylammonio)-2- butenel -sulfonate sodium nitrilotriacetate sodium silicate (Na O:SiO =l l .6)

sodium carboxy methyl cellulose 63% water Balance miscellaneous It will be appreciated that the unsaturated zwitterionic compounds used in the present invention can be incorporated into liquid or granular detergent compositions with suitable adjustments being made in the other components.

Materials which are considered normal and desirable additives in liquid or granule detergent compositions can also be added to the compositions of this invention without substantially modifying the basic characteristics of the unsaturated zwitterionic detergent surfactants. For example, a tarnish inhibitor such as benzotriazole or ethylene thio-urea may be added in amounts up to about 1 percent. Fluorescers, per fume, color, enzymes, antiredeposition agents, thickening agents, opacifiers, other detergent compounds, and blending or viscosity control agents, while not essential in the compositions of this invention, may also be added.

The zwitterionic surface active compounds of the present invention are especially valuable because of their excellent overall soil removing properties. In addition, these compounds possess excellent whiteness maintenance properties when used in combination with the builder compounds described above. Detergency tests have demonstrated that the unsaturated zwitterionic compounds of the present invention provide overall detergency at least equivalent to such an excellent detergent as sodium tallow alkyl sulfate and 3-(coconut alkyl dimethyl ammonio )-2-hydroxy- 1 -sulfonate.

What is claimed is:

1. An unsaturated zwitterionic surface active compound having the formula RzHI-IHH 4-( N,N-dimethyl-N-dodecylammonio)-2-butenel -sul- 

2. An unsaturated zwitterionic surface active compound of claim 1 in which R1 contains eight to 18 carbon atoms, R2 and R3 each contain from one to three carbon atoms.
 3. 4-(N,N-dimethyl-N-alkylammonio)-2-butene-1-sulfonate wherein the alkyl radical ranges from eight to 18 carbon atoms.
 4. 4-(N,N-dimethyl-N-dodecylammonio)-2-butene-1-sulfonate. 